Bis(dicyanophenyl). ethers of dihydric phenols

ABSTRACT

Aryloxy derivatives of aromatic diesters and dinitriles are prepared from reaction of a nitro-substituted phenyl diacid ester or a nitro-substituted phenyl dinitrile with a metal salt of monovalent or divalent aryloxy radicals in the presence of a dipolar aprotic solvent. The invention also includes novel compositions of matter of a difunctional nature prepared in accordance with the above-described process.

United States Patent 1 [111 3,869,499 Heath et a]. Mar. 4, 1975 [5BIS(DICYANOPHENYL). ETHERS 0F 3,567,781 3/1971 Clark 260/465 x 75Inventors: Darrell R. Heath; Joseph G. Wirth,

both of Schenectady, NY.

[73] Assignee: General Electric Company,

' Schenectady, NY.

[22] Filed: Jan. 12, 1973 [21] Appl. No.: 323,083

Related U.S. Application Data [62] Division of Ser. No. 108.151, Jan.20, 1971, Pat. No.

[52] U.S. Cl. 260/465 F, 260/294.9, 260/465 D [5 1] Int. Cl. C07c 121/74[58] Field of Search 260/465 F {56] References Cited UNITED STATESPATENTS 3.4893415 l/l970 Kraus. Jr 260/465 X DIHYDRIC PHENOLS Prinuu')Eranziner-Lewis Gotts Assistant E.rantinerDolph H. Torrence Attorney,Agent, or Firm-Joseph T. Cohen; Jerome C. Squillaro [57] ABSTRACTAryloxy derivatives of aromatic diesters and dinitriles are preparedfrom reaction of a nitro-substituted phenyl diacid ester or anitro-substituted phenyl dinitrile with a metal salt of monovalent ordivalent aryloxy radicals in the presence of a clipolar aprotic solvent.The invention also includes novel compositions of matter of adifunctional nature prepared in accordance with the above-describedprocess.

8 Claims, N0 Drawings BIS(DICYANOPHENYL). ETHERS OF DIHYDRIC PHENOLSThis is a division of application Ser. No. 108,151, filed Jan. 20, 1971,now US. Pat. No. 3,787,475.

This invention is concerned with a process for making aryloxyderivatives of aromatic diesters and dinitriles, and products derivedtherefrom More particularly, the invention relates to a process whichcomprises effecting reaction in the presence of a dipolar aproticsolvent of a mixture of ingredients comprising (1) a benzenoid compoundselected from the class consisting of a. compounds of the generalformula b. compounds of the general formula Z and c. compounds of thegeneral formula III NO where the N group in (a) can be positionedanywhere on the benzene ring and in (c) the N0 group is adjacent to a Zradical, and (2) an alkali metal salt of an organic compound selectedfrom the class consisting of (a) compounds of the general formula R-OAlkand (b) compounds of the general formula AlkOR'-O-Alk where R is amonovalent aromatic radical, R is a divalent aromatic radical, Z iseither -CN or where R" is a monovalent hydrocarbon radical offrom one to12 carbon atoms, and Alk is an alkali metal atom.

The invention is also concerned with compositions of matter selectedfrom the class consisting of a. compounds of the general formula v z z.1Q KI (b) compounds of the general formula and (c) compounds of thegeneral formula where each oxygen in (c) is adjacent to a Z radical in acommonly shared benzene nucleus and where R and Z have the meaningsabove.

Aryloxy derivatives of aromatic diacids have previously been prepared bythree different methods. The most common method consists in effecting acoppercatalyzed reaction between an alkali metal phenolate and a haloaromatic compound followed by oxidation of alkyl substituents tocarboxylic acid groups. Thus, M. M. Koton and F. S. Florinski in Zh.Org. Khim., 4,

(1968) disclose the preparation dioxyphenylene diphthalic acid by thecopper catalyzed reaction of two equivalents of potassium-4,5-dimethylphenolate with 1,4-dibrornobenzene for 4-5 hours at 220-230followed by potassium permanganate oxidation of the methyl groups tocarboxylic acid groups. This method has two major limitations, the firstbeing the known difficulty in reproducing coppcrcatalyzed reactions ofalkali metal phenolates with halo aromatic compounds and and the hightemperatures required to effect these reactions, and the second beingthat any group susceptible to oxidation will be oxidized along with thegroups which are desired to be oxidized.

A second method for preparation of certain arloxy phthalate esters hasbeen disclosed in French Pat. No. 1,573,736 wherein the sodium salt ofdimcthyl-lhydroxyphthalate was caused to react with 4-chloronitrobenzene to give dimethyl4(4-nitrophenoxy)phthalate. Themethod is obviously limited in scope to compounds in which aromatichalogens are highly activated toward nucleophilic displacement. Thethird method involves reaction between a primary aromatic amine withsodium nitrite to give the diazonium salt followed by reaction of thisintermediate with cuprous cyanide to give the aromatic nitrile which maybe hydrolyzed to the acid. This reaction seldom proceeds in high yield,requires handling ofa highly toxic cyanide and is prohibitivelyexpensive for large scale syntheses.

We have without success attempted to effect direct reaction between anitro derivative of an aromatic diacid and an alkali metal phenolate ina dipolar aprotic solvent. For example, the reaction of sodium phenoxideand 4-nitrophthalic acid failed to give any product corresponding to theformula Unexpectedly, we have discovered that although the reactionbetween sodium phenolate and the nitro acid will not take place with3-nitrophthalic acid, nitroterephthalic acid or 2- or 4-nitroisophthalicacid, we are able to make aryloxy derivatives of these acids if reactionis effected between a metal phenolate, such as sodium phenolate, withphthalic, isophthalic or terephthalic acid when the acid is in the formof a nitro ester, for instance, diethyl 4-nitrophthalate or in the formof the corresponding nitrophthalonitrile. This reaction between themetal phenolate and the nitro ester or nitrile usually results in highyield of the phenoxy derivative. The phthalic, isophthalic orterephthalic acids or complex derivatives thereof can then be obtainedby hydrolysis of either the ester group or of the cyano group. In thecase of the aryloxy phthalic acids, various known procedures can be usedfor conversion to the anhydride form.

By virtue of our invention, we are able to prepare numerous di-, triandtetrabasic acids by reaction of a compound of formulas I, II or III witha metal salt of formulas IV or V. In effecting the above reactions, itis important that one use a dipolar aprotic solvent in the reaction ofeither the cyano or ester derivatives of the compounds of formulas I, IIor III. The particular advantages of our invention over the prior artare the mild conditions under which reactions can be carried out, oftenroom temperature is sufficient to effect reaction, generally high yieldof products are obtained, the commercially attractive potential ofsynthesizing aromatic acids containing oxidizable groups (which isimpractical to accomplish by presently known prior art methods), andability to produce diacids and dianhydrides of a broad scope.

Among the monovalent aromatic radicals (this term being intended toinclude organic radicals containing an aryl radical directly attached tooxygen) which R may represent are, for instance, monovalent aromatichydrocarbon radicals of from one to carbon atoms, for instance, aryl(e.g., phenyl, naphthyl, biphenyl, etc.); alkaryl (e.g., tolyl, xylyl,ethylphenyl, etc.); other organic radicals, e.g., organoxyaryl radicals,for instance, methoxyphenyl, phenoxyphenyl, ethoxyethoxyphenyl,ethoxyphenyl; pyridyl radicals, etc. Typical of the hydroxyarylcompounds from which metal salts of formula IV may be prepared byreaction with e.g., an alkali metal, an alkali metal hydroxide orcarbonate may be mentioned for instance:

m-, and p-chlorophenol phenol o-,

and p-aminophenol 2.6-dimethylphenol mo,m and p-cresol m' andp-acetamidophenol land Z-napthol mand p-hydroxybenzoic acid 0- andp-phenylphenol mand p-hydroxybenzonitrile 0-. m-, and p-methoxyphenol3-hydroxypyridine o-, m-. and p-nitrophenol ThydroxyquinolineS-hydroxypyrimidine compound in which the aryl nuclei are joined byeither an aliphatic group, a sulfoxide group, sulfonyl group, sulfur,carbonyl group,- oxygen, the C(CH )(CH CH- CO H) group, etc. Typical ofsuch diarylene compounds from which the metal salt of formula V may beprepared by reacting the aforesaid diarylene compound with two mols ofan alkali metal hydroxide may be mentioned:

2,2-bis-( 2-hydroxyphenyl )propane; 2,4'-dihydroxydiphenylmethane;bis-(2-hydroxyphenyl)-methane; 2,2-bis-(4-hydroxyphenyl)-propanehereinafter identified as bisphenol-A or BPA;bis-(4-hydroxy-5-nitrophenyl)-methane;bis-(4-hydroxy-2,6-dimethy1-3-methoxyphenyl)- methane;l,1-bis-(4-hydroxyphenyl)-ethane; l, l-bis-(4-hydroxy-2-chlorophenyl)-ethane;1,l-bis-(2,5-dimethyl-4-hydroxyphenyl )-ethane; l,3-bis-(3-methyI-4-hydroxyphenyl )-propane;2,2-bis-(3-phenyl-4-hydroxyphenyl)-propane;2,2-bis-(3-isopropyl-4-hydroxyphenyl)-propane;2,2-bis-(4-hydr0xynaphthyl)-propane; 2,2-bis-(4-hydroxyphenyl)-pentane;3,3-bis-(4-hydroxyphenyl)-pentane; 2,2-bis-(4-hydroxyphenyl)-heptane;bis-(4-hydroxyphenyl)-phenylmethane;bis-(4-hydroxyphenyl)-cyclohexylmethane; l,2-bis-(4-hydroxyphenyl)-l,2-bis-(phenyl propane; 2,2-bis-(4-hydroxyphenyl)-l-phenylpropane;

2,4-dihydroxybenzophenone; 4,4'-dihydroxydiphenyl sulfone;2,4'-dihydroxydiphenyl sulfone; 5-chloro-2,4'-dihydroxydiphenyl sulfone;3-chl0ro-4,4'-dihydroxydiphenyl sulfone; 4,4-dihydroxytriphenyldisulfone; 4,4'-dihydroxydiphenyl ether; 4,4'-dihydroxydiphenyl sulfide;4-hydroxy-o-biphenyl ether; the 4,3'-,4,2'-,4,1'-,2,2- 2,3'-, etc.dihydroxydiphenyl ethers; 4,4'-dihydroxy-2,o-dimethyldiphenyl ether;4,4-dihydroxy-2,S-dimethyldiphenyl ether;4,4'-dihydroxy-3,3'-diisobutyldiphenyl ether;2-methyl-2-carboxy-bis-(4-hydroxyphenyl)-propane;4,4-dihydroxy-3,3-diisopropyldiphenyl ether;4,4'-dihydroxy-3,2'-dinitrodiphenyl ether;4,4'-dihydroxy-3,3'-dichlorodiphenyl ether;4,4-dihydroxy-3,3'-difluorodiphenyl ether; 4,4-

dihydroxy-2,3'dibromodiphenyl ether; 4,4-dihydroxydinaphthyl ether;4,4-dihydroxy-3,3'-dichlorodinaphthyl ether; 2,4-dihydroxytetraphenylether; 4,4-dihydroxypentaphenyl ether;4,4'-dihydroxy-2,6-dimethoxydiphenyl ether;4,4'-dihydroxy-2,S-diethoxy-diphenyl ether, etc., di-

hydric phenols substituted on the aryl nucleus with alkyl, alkenyl,cycloaliphatic, cycloalkenyl, aryl, alkaryl, numerous examples of whichhave been given above as well as the dihydroxy toluenes, the dihydroxyxylenes dihydroxy pyridines, dihydroxy anthraquinones, dihydroxy benzoicacids, dihydroxy benzophenones, etc. The R and R radicals can also haveinert substituents on the aryl nuclei, for instance, monovalenthydrocarbon radicals such as methyl, ethyl, cycloaliphatic radicals (forinstance, cyclopentyl, cyclohexyl etc.), etc.; aryl radicals, e.g.,phenyl, biphenyl, etc., radicals; alkaryl radicals, e.g., tolyl,ethylphenyl, etc., radicals; aralkyl radicals, e.g., benzyl,phenylethyl, etc., radicals. The substituent on the aryl radicalaccordingly can be any one which does not constitute or contain an atomor radical reactive with the alkali metal salt of either formula IV orformula V.

Since the radical R" may eventually be removed through hydrolysistechniques in order to obtain a carboxy group, R" is a monovalenthydrocarbon radical of from one to 12 carbon atoms which is not criticalin the process herein described. Thus, R" may be an alkyl radical, forinstance, methyl, ethyl, propyl, isobutyl, hexyl, 2-ethylhexyl, etc.; anaryl radical, for instance, phenyl, biphenyl, etc.; an aralkyl radical,for instance, benzyl, phenylethyl, etc.; an alkaryl radical, forinstance, tolyl, ethylphenyl, etc. Preferably R is an alkyl radical offrom two to four carbon atoms.

The means whereby the process of the present invention may be practicedand compositions herein defined obtained can be varied widely and to aconsiderable extent depend on whether a monoalkali metal salt of thegeneral formula IV or a dialkali metal salt of the general formula V areemployed. When a monoalkali metal salt of formula IV is used, generally1 mol of the latter per mol of the compound of formulas I, II or III isadvantageously used. Obviously the molar ratio of these two ingredientsmay be varied widely and broadly from 1 to up to 3 or more mols of themetal salt of formula 1V per mol of the benzenoid compound of formula 1can be employed. Generally no advantage is obtained in using an excessof the metal salt with the exception that the reaction may be promotedin the direction of higher yields and greater completion.

On the other hand when dialkali metal salts of formula V are used withthe benzenoid compound of formulas I, II or III, the molar ratio isadvantageously at least 2 mols of the compound of general formula I, IIor 111 per mol of the metal salt of formula V. Excess molar quantitiesof the compound of formulas I, II or 111 over the molar quantity of themetal salt of formula V may be employed without departing from the scopeof the invention; thus from 2 to 4 or more mols of the compound offormulas I, II or 111 may be used per mol of the metal salt of formulaV.

In making the metal salts of formulas IV and V, it is sometimesadvantageous to preform these salts by reacting the correspondingmonohydroxy organic com pound or dihydroxy organic compound with analkalimetal hydroxide such as sodium hydroxide, potassium hydroxide,etc. For instance. sodium phenate may be obtained by reacting in amanner well known in the art, 1 mol sodium hydroxide per mol of phenol.By the same token, the dialkali salt of bisphenol-A may be obtained, forinstance, by reacting 2 mols of sodium hydroxide per mol of bisphenol-A.Persons skilled in the art will have no difficulty in determining how tomake the alkali-metal salts of formulas IV and V for use with thecompounds of formulas I, II or III.

Alternatively, the phenol or bisphenol may be converted to its alkalimetal salt during reaction with compounds of formulas I, II or III byaddition of an alkali metal carbonate in adequate molar concentrationsto a reaction mixture composed of the compound of formula I, 11 or IIIand the precursor hydroxy aromatic compound required to form the metalsalts of formulas IV or V.

The conditions of reaction whereby the metal salts of formulas IV and Vare reacted with the compounds of formulas I, II or III can be variedwidely. Generally, temperatures of the order of about 20 150 C. areadvantageously employed, although it is possible to employ lower orhigher temperature conditions depending on the ingredients used, thereaction product sought, time of reaction, solvent employed, etc. Inaddition to atmospheric pressure, superpressures and subatmosphericpressures may be employed depending upon the other conditions ofreaction, the ingredients used, the speed at which it is desired toeffect reaction, etc.

The time of reaction also can be varied widely depending on theingredients used, the temperature, the desired yield, etc. It has beenfound that times varying from a few minutes to as much as 30 to 40 hoursare advantageously employed to obtain the maximum yield. Thereafter thereaction product can be treated in the manner required to effectprecipitation and/or separation of the desired reaction product.Generally, common solvents such as diethyl ether, water, etc., areemployed for the purpose. For purification purposes, the final productcan be redistilled or recrystallized in manners Well known in the art.

It is important that the reaction between the compounds of formulas I,II or III and the metal salts of formulas IV or V be carried out in thepresence of a dipolar aprotic solvent. The term dipolar aprotic solvent"is intended to mean any organic solvent which has no active protonswhich may interfere with the reaction herein described. As will beevident to those skilled in the art, any dipolar aprotic solvent whichis capable of dissolving the reactants and causing intimate contact ofthe reaction ingredients may be used.

Among the preferred aprotic solvents which may be employed in thepractice of this invention are non-acid, oxygen-containing,nitrogen-containing organic solvents. These include but are not limitedto, for instance, N,N -dimethylacetamide, N-methylpyrrolidone, N,N-dimethylformamide, dimethylsulfoxide, etc.

The amount of solvent used in the reaction mixture may be varied widely.Generally, on a weight basis, one can employ from 0.5 to 50 or moreparts of the solvent perpart of total weight of the reactants, namely,the compounds of formulas I, II or III and the metal compounds offormulas IV or V. The amount of solvent is not critical, but generallywe have found that on a weight basis one can employ from 2 to 20 partsof the solvent per part of the total weight of the compounds of formulasI, II or III and the metal compounds of formula IV or V.

In order that those skilled in the art may better understand how thepresent invention may be practiced, the following examples are given byway of illustration and not by way of limitation. Unless otherwisestated, all parts are by weight.

EXAMPLE 1 A mixture of 1.034 grams (0.011 mol) phenol, 0.4 gram (0.01mol) sodium hydroxide (0.7905 gram of 50.6 percent aqueous solution), 20ml. dimethylsulfoxide (DMSO), and 10 ml. toluene was stirred at refluxtemperature under nitrogen over a DeanStark trap for 4 hours. Thereaction mixture was cooled to C.,

2.67 grams (0.01 mol) diethyl 4-nitrophthalate was added and thesolution was stirred under nitrogen atmosphere at 100-110 C. for 3hours. The reaction mixture was poured into 300 ml. of water and theproduct was extracted into ether. The ether extracts were combined,washed with water, 1 percent sodium hydroxide aqueous solution, driedwith sodium sulfate, filtered, and the ether was removed. The productwas distilled at 150160 C. (0.15 mm) to yield 3.0 grams (95.5 percentyield) ofa liquid which was identified by infra red examination and byelemental analyses as diethyl 4-phenoxyphthalate.

Found Calculated EXAMPLE 2 To ml. anhydrous DMSO was added 0.119 gram(0.001 mol) 2-cyanophenol, 0.173 gram (0.001 mol) 4-nitrophthalonitrileand 0.138 gram (0.001 mol) anhdyrous potassium carbonate. After stirringfor hours at room temperature, the reaction mixture was poured intowater. Extraction of the product into ether followed by drying of theextract with sodium sulfate, solvent removal and recrystallization fromethanolwater gave 0.168 gram (69 percent) 2,3,4- tricyanodiphenylether,melting point l34-136 C. The product was identified by its spectroscopicproperties, infra red. and by mass spectral analysis.

EXAMPLE 3 EXAMPLE 4 A mixture of 1.09 grams (0.01 mol) 3-aminophenol,2.67 grams (0.01 mol) diethyl-4-nitrophthalate, 1.38 grams (0.01 mol)potassium carbonate, and 20 ml. DMSO was stirred under a nitrogenatmosphere at 100 C. for 24 hours and was then allowed to cool. The DMSOsolution was poured into water and the product was extracted into ether.The ether extract was washed with water, dried with sodium sulfate,filtered, and the ether was removed to leave an oily liquid.Distillation of this liquid at 220 C. (0.15 mm) gave 2.1 grams (64percent) of liquid diethyl-4-(3-aminophenoxy)phthalate, whose identitywas established by infra red and nmr.

EXAMPLE 5 A mixture of 0.41 gram (0.00375 mol) 4- aminophenol, 1 gram(0.00375 mol) diethyl 4- nitrophthalate, 0.525 gram (0.00375 mol)potassium carbonate, and 10 ml. dry DMSO was stirred under a nitrogenatmosphere at about 1 10 C. for 48 hours and then allowed to cool. Thereaction mixture was poured into water and the product was extractedinto ethyl ether. The ether extract was washed with water, dried withsodium sulfate, filtered, and the ether was removed to leave an oilyliquid which was distilled at 200210 C. (0.1 mm) to give 1.18 grams (96percent) of a liquid which crystallized slowly on standing at roomtemperature. The distilled product was recrystallized from ethanol-waterto give long white needles which had a melting point of 7476 C. Thismaterial was identified by infra red, nmr and by elemental analyses asdiethyl-4-(4-aminophenoxy)phthalate.

A mixture of 0.94 gram (0.01 mol) phenol, 0.40 gram (0.792 gram) 50.5percent aqueous solution, 0,01 mol) sodium hydroxide, 20 ml. ofanhydrous DMSO which had been sparged with nitrogen. and 10 ml. ofbenzene was stirred at reflux under nitrogen over a Dean-Stark trap for4 hours and the benzene was removed by distillation. The DMSO solutionwas cooled to 50 C. and 1.73 grams (0.01 mol) of 4- nitrophthalonitrilewas added. The mixture was stirred under nitrogen at room temperaturefor 15 minutes and was then poured into 100 ml. of water. The productwas extracted from the aqueous solution into ether and the ether extractwas washed with water, dried with sodium sulfate and filtered. The etherwas removed to leave a white solid which was distilled at 165 C. (0.15mm) to give 2.10 grams (95.5 percent of pale green solid.Recrystallization from absolute ethanol gave white needles which werefiltered and dried in vacuo; melting point 100-101 C. This product wasidentified as 4-phenoxyphthalonitri1e by infra red and by elementalanalyses.

Found Calculated AC 76.3 76.4 71H 3.60 3.64 IYIIN 12.7 12.72

EXAMPLE 7 recrystallized from acetonitrile to give 3.65 grams (69percent) of fine pale blue-green needles, melting point l67-168 C. Thisproduct was identified as 4-(3-nitrophenoxy)phthalonitrile by infra redand by elemental A sodium phenoxide solution in dimethyl sulfoxide(DMSO) was prepared by addition of 0.94 gram (0.01 mol) phenol to 0.8gram (0.01 mol) 50 percent aqueous sodium hydroxide in 20 ml. DMSO andwarming to 70 C. Toluene, 20 ml. was added and water was removed byazeotropic distillation. The system was maintained in a nitrogenatmosphere. When the solution was anhydrous, toluene was distilled outand 2.67 grams (0.01 mol) diethyl nitroterephthalate was added. Afterheating for 6 hours at 100 C., the solution was poured into water andthe product extracted into ether. The extract was dried with sodiumsulfate, concentrated to small volume and distilled in a kugelrohr. Thefraction which distilled at l50-l60 C./0.1 mm weighing 2.6 grams (86percent) was collected. This product was identified asdiethylphenoxyterephthalate by nmr and by mass spectrum.

EXAMPLE 9 A sodium phenoxide solution in dimethylsulfoxide preparedsimilarly as in Example 8 was mixed with 20 ml. toluene and water wasremoved by azeotropic distillation while the system was maintained in anitrogen atmosphere. When the solution was anhydrous, toluene wasdistilled out and 2.67 grams (0.01 mol) diethyl-2- nitroisophthalate wasadded. After heating for 3 hours at 100 C., the solution was poured intowater and the product extracted into ether. The extract was dried withsodium sulfate, concentrated to small volume and distilled in akugelrohr. The fraction which distilled at l50l60 C. weighing 2.75 grams(91 percent) was identified as diethyl-2-phenoxyisophthalate by nmr andmass spectrum.

EXAMPLE 10 To 10 ml. DMSO were added 1.34 grams (0.005 mol) diethyl4-nitrophthalate and 0.68 grams (0.01 mol) sodium ethoxide. Theresultinng solution was stirred for about 18 hours and then poured intowater. The product was extracted into ether and the extract was driedwith sodium sulfate. Solvent removal left an oil which was distilled at170 C./0.l mm to give 0.60 gram (45 percent) diethyl-4-ethoxyphthalatewhose identity was established by nmr.

EXAMPLE 1 1 1,4-Bis(3,4-dicarboethoxyphenoxy)benzene was prepared asfollows. A mixture of 2.67 grams (0.01 mol) diethyl-4-nitriphthalate,0.55 gram (0.005 mol) hydroquinone, 1.38 grams (0.01 mol) potassiumcarbonate, and 20 ml. dry DMSO was stirred under nitrogen at 100 C. for48 hours. The reaction mixture was poured into water and the product wasextracted from the aqueous solution into diethyl ether. The etherextract was washed with water, 1 percent hydrochloric acid solution, 1percent sodium hydroxide solution, treated with decolorizing carbon,dried with sodium sulfate, filtered, and the ether removed. The producewas distilled at 220-250 C. (0.1 mm) to give 1.45 grams (53 percent) ofoil which was dissolved in 30 ml. of warm absolute ethanol and theproduct separated from solution at 0 C. as fine white needles which werefiltered cold and dried in vacuo, melting point 4850 C. Identity of theproduct was established by infra red and by elemental analyses.

Bis( 3,4-dicyanophenyl)ether of bisphenol-A was prepared as follows. Amixture of 1.71 grams (0.0075 mol) bisphenol-A, 0.6 gram (1.1881 grams50.5 percent aqueous solution, 0.015 mol) sodium hydroxide, 20 ml.nitrogen-sparged DMSO, and 15 ml. benzene was stirred at reflux undernitrogen over a Dean-Stark trap for 4 hours and the benzene was thenremoved by distillation. The reaction mixture was cooled to roomtemperature and 2.595 grams (0.015 mol) 4- nitrophthalonitrile wasadded. The mixture was stirred under nitrogen at room temperature for1.5 hours and was then poured into 100 ml. of water. The product whichseparated from the aqueous solution as a white powder was extracted intomethylene chloride and the extract was washed with water, dried withsodium sulfate, and filtered. The solvent was removed and the residuewas recrystallized from toluene/hexane solution to give 3.1 grams (86percent yield) of a white grannular solid, melting point l95196 C. Thisproduct was identified as the above compound by infra red and byelemental analyses.

Found Calculated C 77.6 77.5 %H 4.24 4.17 %N l 1.8 l l .66

This compound had the formula CN o@ca, @O 2 EXAMPLE 131,4-Bis(3,4-dicyanophenoxy)benzene was prepared by first forming amixture of 1.10 grams (0.01 mol) hydroquinone, 3.56 grams (0.02 mol) 4-nitrophthalonitrile, 2.76 grams (0.02 mol) anhydrous potassiumcarbonate, and ml. of dry, nitrogensparged DMSO. This was stirred undernitrogen at room temperature for 24 hours and the mixture was pouredinto 200 ml. of water. The precipitate was filtered, washed with water,dried in vacuo" and dissolved in 250 ml. boiling acetonitrile. Theproduct crystallized from the acetonitrile as fine pale blue needlesamounting to 2.2 grams (6lpercent yield). The crystallized product wasdistilled at 3003 10 C. (0.05 mm) to yield an oil which solidified oncooling. This solid material was recrystallized from acetonitrile togive 2.1 grams of the desired compound, melting point 255257 C. whoseidentity was established by infra red and by elemental analyses.

Found Calculated /:C 72.7 72.9 21 H 2.70 2.75 1 N 15.6 1545 O- C=O O=C 00 j 0 EXAMPLE 14 A mixture of 0.93 gram (0.005 mol) 4,4-dihydroxybiphenyl, 0.4 gram (0.792 gram of 50.5 percent aqueoussolution, 0.01 mol) sodium hydroxide, ml. nitrogen-sparged DMSO, and 20ml. benzene was stirred under a nitrogen atmosphere at refluxtemperature over a Dean Stark trap for 18 hours and the benzene was thenremoved by distillation. The mixture was cooled to room temperature,1.73 grams (0.01 mol) 4- nitrophthalonitrile was added; and stirringunder nitrogen at C. was continued for 40 hours. The mixture was pouredinto 200 m1. of water and the product, a white granular solid, wasfiltered and washed with water. Recrystallization from acetonitrile gave2.10 grams of product (96.0 percent yield), melting point 233233.5 C.The identity of the product as 4,4-bis- (3,4-dicyanophenoxy)biphenyl wasestablished by infra red and by elemental analyses.

EXAMPLE 15 A mixture of 0.723 gram (0.005 mol) 2- chlorohydroquinone,1.73 grams (0.01 mol) 4- nitrophthalonitrile, 1.38 grams (0.01 mol)potassium carbonate, and 15 ml. dry nitrogen-sparged DMSO was stirredunder a nitrogen atmosphere at room temperature for 40 hours. Thesolution was poured into water and the precipitate which separated wasisolated by filtration, washed with water, dried in vacuo, and distilledat 230 C. (0.05 mm) to give 1.8 grams (9lpercent yield) of an oilyliquid which solidified on cooling to form a white solid. The distilledproduct was recrystallized from acetonitrile to give fine white needles,melting point 204205.5 C. The product was identified as2-chloro-1,4'bis-(3,4dicyanophenoxy)benzene by infra red and byelemental analyses.

dihydroxydiphenyl sulfone, 0.4 gram (0.791 gram 50.5percent aqueoussolution, 0.01 mol) sodium hydroxide, 20 ml. nitrogen-sparged DMSO, and20 ml. of benzene was stirred under nitrogen atmosphere at reflux over aDean Stark trap for 18 hours and the benzene was removed bydistillation. The mixture was cooled to room temperature and 1.73 grams(0.01 mol) of 4-nitrophtha1onitrile was added and stirring was continuedat room temperature (about 2628 C.) in air for 40 hours. The homogeneoussolution thus obtained was poured into 200 ml. of water and theprecipitate which separated was isolated by filtration, washed withwater, dried in vacuo and recrystallized from acetonitrile. The productseparated from the cooled solution as golden needles and was filteredand dried in vacuo to give 1.5 grams (60percent) yield, melting point229-230 C. of 4,4'-bis-(3,4-dicyanophenoxy)diphenylsulfone. The productwas identified as such by infra red and by elemental analyses.

A mixture of 1.01 grams (0.005 mol) 4,4'-dihydroxydiphenyloxide, 0.4gram (0.792 gram SOpercent aqueous solution, 0.01 mol) sodium hydroxide,20 ml. nitrogen-sparged DMSO, and 20 ml. benzene was stirred undernitrogen at reflux over a Dean Stark trap for 18 hours and the benzenewas removed by distillation. After cooling to room temperature, 1.73grams (0.01 mol) of 4-nitrophthalonitrile was added and the mixture wasstirred under nitrogen at room temperature for 15 hours and then pouredinto 200 ml. of water. The product was extracted from the aqueoussolution into methylene chloride. The extract was washed with water,dried with sodium sulfate, filtered, and the solvent was removed toleave a white solid which was recrystallized from aqueous acetonitrileto give 1.6 grams (58percent yield) of white needles. This product was Amixture of 1.22 grams (0.01 mol) 3,4-dimethyl phenol, 0.4 gram (0.792gram 50.5percent aqueous solution, 0.01 mol) sodium hydroxide, 15 ml.nitrogensparged DMSO, and 15 ml. benzene was stirred at reflux undernitrogen over a Dean Stark trap for 4 hours and the benzene was removedby distillation. The reaction mixture was cooled to 40 C. and 2.67 grams(0.01 mol) diethyl 4-nitrophthalate in 5 ml. dry, nitrogensparged DMSOwas added and the mixture was stirred under a nitrogen atmosphere atroom temperature for 64 hours. The reaction was quenched by pouring intowater and the product, which separated as an oil, was extracted intodiethyl ether. The ether extract was washed with water, aqueous sodiumbicarbonate solution. dried with sodium sulfate, filtered, and the etherwas removed to leave a yellow oil. Distillation of this oil at l65-175C. (0.025 mm) gave 3.0 grams (88percent) of a liquid identified by infrared and by nmr as 4-( 3 ,4-dimethylphenoxy )diethylphthalate.

EXAMPLE 19 Found Calculated 21C 77.1 77.4 '/(H 3.5 3.13 /rN 12.3 12.4

EXAMPLE 20 To a mixture of 1.07 grams (0.004 mol) diethyl2-nitroisophthalate, 0.22 gram (0.002 mol) hydroquinone and 0.55 gram(0.004 mol) potassium carbonate was added ml. nitrogen-sparged DMSO. Theresulting mixture was heated at 100 C. for 48 hours and then poured intowater. The product separated as an oil and was extracted into ether. Theextract was washed with water, dried over sodium sulfate andconcentrated. Distillation of the residue at 250 'C/0.1 mm gave 060 gram(55percent) of 1,4-bis-(2,6-dicarboethoxyphenoxy)benzene whichcrystallized on cooling, melting point l02-l03 C., and was identified byinfra red. nmr spectra and by elemental analyses.

Found Calculated This compound had the formula 00 C 11 CO C H 49% 0 C0 CH 0 0 1-1 EXAMPLE 21 To a mixture of 2.67 grams (0.010 mol) diethylnitroterephthalate, 0.55 gram (0.005 mol) hydroquinone and 1.38 grams(0.010 mol) potassium carbonate was added 20 ml. nitrogen-sparged DMSO.The resulting mixture was heated for 48 hours at C. and then poured intowater. The product separated as an oil and was extracted into ether. Theextract was washed with water, dried over sodium sulfate andconcentrated to small volume. Distillation of the residue at 250 C./0.lmm gave 0.75 gram (27perceint) of l,4-bis(2,5-dicarboethoxyphenoxy)benzene which crystallized on cooling, meltingpoint 124-125 C'., and was identified by infra red, nmr spectra and byelemental analyses.

Employing the same conditions as are recited in Examples 1 and 6, othercompositions can be prepared by sutstituting other reactants of formulasl, [l or III in place of the corresponding reactants in these examples,and other reactants of formula IV in place of the corre sponding metalsalts used in these earlier examples. The foillowing Table 1 recitessome of the reactants which can be employed to form these compositions.The heading Reactant A corresponds to the compound of formula 1, II orIII which can be used and the heading Reactant B corresponds to theprecursor hydroxy compound of formula IV. The products derived lattertwo examples. The following Table II recites some of the-reactants whichcan be employed to form products coming within the scope of formula VI.The

definitions ofReactant A, Reactant B, Product TABLE I Sumplc No.React-ant A Reuctunt B Product I DicthyI-4-nitrophthulute p-PhenylphenolDicthyl 4-(4-phenylphenoxy)phthulntc 2 Dicthyl-B-nitrophthulutep-Chlorophenol Diethyl-3-(4 chlnrophcnoxy)phthzllutc 34-Nitrophthalonitrile p-Crcsol 4-(4-Methylphenoxy)phthulonitrile 4l-Nitrophthulonitrilc pAminophenol 3-(4-Aminophenoxy)phthulonitrile 5Diethyl-nitroterephthulute m-Hydroxybcnzoic AcidDiethyl4-czirhoxyphenoxytcrcphthulute 6 NitroterephthnlonitrileJ-Nitrophenol 4-Nitrophcnoxytcrcphthnlonitrilc 7Diethty]-2-nitroisophthulutc p Hydroxybenzoic AcidDielhyl-2-(4-curhoxyphcnoxy X Diethyl-4-nitroisophthulutc Same as 5Dlclh l-4 ("Lcurhoxyphenoxy 9 2-Nitroisophthulonitrilep-Hydroxybenzuldehydc 2-(4-curboxuldehydophenoxy)isophthulonitrilc4-Nitroisophthulnnitrilc p-Nitrophcnol EXAMPLE 23 4-( 4 nitrophcnoxy)isophthulonitrilc and the designation Et are the same as those recitedfor the equivalent terms in Example 22.

EXAMPLE 24 Employing the same conditions as recited in Example 21, othercompositions can be prepared coming within the scope of formula VII,substituting other reactants O 20 U W N ollq ocwuuomum q no 05mm S Z0 Z0$6 w um owocmucmm zu o AW N E3 993 m I 9.37 #J m mm 08mm ZJ NANEWV 33 AHfl U S Qv m-8 AHY U A Q MHHN O mfloconmoucmnxxouwxswa 2 3 Q mm mEmm 3 Z0Z0 o 5 2o m m zo wwov o i o Amw oz mo om m we 3 2 be ew 96 oz 5 3 5 WW No m WW N 42 5 i nfi ifin- 3 N me m 2 w en E S 6 8 u oum m m 5 m6 N 8 5 8MWV o A wv u o AWNo one ago: A we 25m 3 5 8 $6 $6 Q Q E oz m uumuumum 4ucmuommm uon oum mfiafimm 2 52.

i which can be employed to form products coming of formula [I in placeof the corresponding reactant in 65 within the scope of formula VII, Thd fi i i ofR Example 21, and other reactanats of formulae V in actant A,Reactant B, Product and the designaplace of the metal salt used in theearlier Example 21. tion Et are the same as those recited for theequiva- The following Table III recites some of the reactants lent termsin Example 22.

u u v )g D m u 2 ON M 2 U u U o 0 O z Z 0 m U 0 O u a: O

N o 5 O O O O m ("1 m m 5 U 33 2 U -U- Q: O O 'o o 3 [:F l

Ll (C; m o z O k m N 1 II.

o L t-l 8 O U Q N O z 0 u z z 8 U BI U U o 0 {3 165 O O Z N U z o D Z OU 2 H H E H m H .C. (:J .3 ES 4 1 2 (U x H pq G O \l \O 0 r-4 Li q 44 F4--1 Pl (:1 .-4. I: O "-1 VH as c. u) m :1 w J: x U Q) U (U U" I Q U .C 03 a a a a a a a: -H m m as I an m m :c: m

m \D m \o to to I U] U! II) I!) w t!) cu m m m m m cu 1) w m cu cu m cum l? 5% 5 l3 5 5% m w m m tn 0:

ca o co m o -i N m 5 Z H N N N N m EXAMPLE 25 of the metal salt used inthe earlier Example 20. The following Table IV recites some of thereactants which Employing the same conditions as recited in Example canbe employed to form products coming within the 20, other compositionscan be prepared coming within 65 scope of formula VIII. The definitionsofReactant A," the scope of formula VIII, substituting other reactantsReactant B, Product and the designation Et are of formula III in placeof the corresponding reactant in the same as those recited for theequivalent terms in Example 20, and other reactants of formula V inplace Example 22.

, 2 m6 I MM MEN mm MEN ze AHw An vv m. o WWVV QZ 2 m S m S m zo z zu o WwV mm mm mBmm m mm mamm mm oz zu o l w 8m mm mam w Amv ofi oz 3 mm m 3 mR Z0 0 Zn oz zo U o WHV 0 mm mEmm 0 mm mEmm ow OZ ZU 5 8 5 8 -05 5 5 8 oO WWMV & mm mEmm 5 mm 08mm q o o m mu 5 8 uuflwoum m ucmuuwmm 4 ucmuommmoz 295m B 0E5.

The following examples illustrate the unsuccessful liquid chromatographyof the solution showed only the attempts to make arloxy derivaatives ofaromatic diacbistrimethylsilyl ester of 4-nitrophthalic acid. Not evenids by direct reaction of a metal phenolate with the trace amounts ofthe bistrimethylsilyl ester of 4- nitro diacids instead of the nitroesters or nitro nitriles phenoxyphthalic acids were obtained. Continuedheatas is called for in the present invention.

ing for an additional 24 hours at 100 C. also failed to of the formationof 4- show any evidence phenoxyphthalic acid.

EXAMPLE A To a solution of 1.16 grams (0.010 mol) sodium phenoxide in 10ml. DMSO was added 0.70 gram (0.003 mol) 4-nitrophthalic acid and theresulting soluphenoxide in 10 ml. DMSO was added 0.70gram (0.003 mol)nitroterephthalic acid and the resulting sotion was heated for 24 hoursat C. A portion of the solution was withdrawn, neutralized withhydrochloric acid and bistrimethylsilylacetamide was added. Gaslutionwas heated for 24 hours at l00 C. A portion of again failed to produceany of the latter compound.

EXAMPLE C To a solution of 1.16 grams (0.010 mol) sodium phenoxide inml. DMSO was added 0.70 gram (0.003 mol) 2-nitroisophthalic acid and theresulting solution was heated for 24 hours at 100 C. A portion of thesolution was withdrawn, neutralized with hydrochloric acid andbistrimethylsilyacetamide was added. Gas-liquid chromatography of thesolution showed only the bistrimethylsilyl ester of l-nitroisophthalicacid indicating that no 2-phenoxyisophthalic acid was obtained.Continued heating for an additional 24 hours at 100 C. also failed toshow any displacement by phenoxide radicals.

The compositions herein described and taught and produced in accordancewith the invention embraced by the claims have many uses. Olne of themore important uses to which these compositions may be put are asintermediates in the preparation of other compositions of matter. Inaddition, many of the compositions herein described and taught,particularly those which are liquid at room temperature, may haveapplication per se as solvents in the preparation of other organiccompositions. Furthermore, referring to the simple aryloxy diestersembraced by the compositions obtained, for instance, in Examples 1 to 10the diesters can be hydrolyzed to give the corresponding dicarboxyderivatives or the dicyano groups can be hydrolyzed to again give thecorresponding dicarboxy groups and these dicarboxy substituted compoundscan be reacted with long chain monohydric alcohols, for instance, 2-ethylhexanol to give ester compositions which are useful as plasticizersfor vinyl halide resins, for instance, polyvinyl chloride resins.

More particularly, taking as a specific example, one can treat thecompound, diethyl-4- phenoxyphthalonitrile in Example 6 simultaneouslywith anhydrous HCl and approximately two molar equivalents ofZ-ethylhexanol to give the corresponding diester having the formulawhich can be used for plasticizing vinyl halide resins, etc. Again,diethyl-4-phenoxyphthalate of Example 1' boxy compositions can beemployed is in the preparation of polyester polymeric compositions. As aspecific instance, the diethyl-Z-phenoxyisophthalate of Example 9 can becaused to react with l,4-butanediol in a manner well known to thoseskilled in the art to give the corresponding polyester which can be caseinto films useful for packaging purposes.

The triand tetra-functional compositions obtained in accordance with thepractice of the present invention can be reacted in a manner designed toeffect hydrolysis and esterifieation with the appropriate ingredientssimilarly as described above. Additionally. the L4-bis-(3,4-dicarboethoxyphenoxy)benzzene of Example 1 1 can be hydrolyzedin the usual fashion to remove the ethyl groups on either end and toobtain the corresponding tetracarboxy compound of the formula HO C 0 1-!HO C This composition can then be dehydrated to give the correspondingdianhydride which can be used to cure epoxy resins.

The bis(3,4dicyanophenyl)ether of Bisphenol-A (Example 12) can betreated to effect hydrolysis of the nitrile groups and the correspondingtetracarboxy ether can be reacted with long chain monohydric alcohols ina molar ratio of4 moles of the monohydric alcohol per mole of thetetracarboxy ether. Such an ester can also be used for plasticizingpolyvinyl chloride resins. If there is an ester group instead of anitrile group on an. aryl nucleus, the ester group can be hydrolyzed ina 'manner well knoiwn to those skilled in the art to give thecorresponding carboxy group and then treated for esterification purposesin the manner described previously. In a similar manner, othercompositions coming within the scope of formulas VI, VII and VIII can beconverted into esters which can be used for plasticizing polyvinylchloride resins.

One of the more important uses of compositions prepared by means of thepresent invention is as intermediates in the preparation ofheat-resistant polyimides, which have many known uses. Specifically, thediethyl- 4-(3-aminophenoxy)phthalate of Example 4 can beself-polymerized to a polyimide by hydrolysis to the diacid followed byheating in a suitable solvent such as N-methylpyrrolidone. Anotherspecific example of polyimide preparation utilizes4,4'-bis(3,4-dicyanophenoxy)diphenyl oxide of Example 17. Hydrolysis ofthe nitrile groups to carboxy groups and dehydration of these by heatingor reaction with acetic anhydride gives the dianhydride which can becaused to react with an aromatic diamine, such as 4,4-diaminodiphenyloxide, to give an aromatic polyimide. Other compositions coming withinthe scope of formula VI can be employed similarly in the preparation ofpolyimides in a similar fashion.

Polymers having mixed functional groups, specifically polyesterimidesand polyamideimides, can be prepared from compositions coming within thescope of the present invention. These materials have many uses asinsulating materials. The 2,3, 4-tricyanodiphenyl ether of Example 2 canbe hydrolyzed to the corresponding tricarboxy ether and converted to apolyesterimide or polyamideimidc in a manner well known to 3,869,499 2526 those skilled in the art. (a)

In addition to the utilities described previously for polymericcompositions derived from the difunctional aryloxy compounds describedand taught in the present application, these polymeric compositions canalso have other applications. These polymeric compositions may be usedto form fibers, films, or molded products. Thus, either by extrusionfrom melt or by depositing from solution, fibers derived from thesepolymeric z compositions may be formed and used in the preparation ofvarious textile materials designed for clothing and similarapplications. In addition, solutions of the O O polymers can be used tocoat electrical conductors for insulation purposes. Z

Various fillers may be incorporated in the polymeric compositions priorto molding thereof. Among such and fillers may be mentioned glassfibers, carbon black, ti- (c) tanium dioxide, silica, mica, bentonite,etc. Molded Z products derived from such a mixture of ingredients can beused as gears, handles for cooking utensils, etc. The incorporation ofabrasive particles such as carbo- Z rundum, diamond powder, etc., makesmolded products derived from such polymeric compositions useful asgrinding wheels, etc. The addition of carbon, silicon carbide, powderedmetal, conducting oxides, etc., to where each oxygen in (c) is adjacentto a Z radical in the polymeric compositions results in the so-calledrea Commonly shared benzene nucleus and where R is a sistance orsemiconducting paints which have many divalent afOmatic radical, Z isthe radicalscf l li ti 2. A compound as in claim 1 which has the generalThe polymeric compositions herein described may formula also beincorporated into other materials to modify the properties of thelatter. For example, they may be com- Z Z pounded with substances suchas natural or synthetic Z O RI 0 Z rubbers, natural resins such asrosin, copal, shellac,

etc.; synthetic resins such as phenol-aldehyde resins,

alkyd resins, vinyl resins, esters of acrylic and methwhere Z and R havethe meanings defined in claim 1.

acrylic acid, etc.; cellulosic materials such as paper, in- 3. Acompound as in claim 1 having the general fororganic and organic estersof cellulose such as cellulose mula nitrate, cellulose acetate,cellulose ethers, such as Z Z methyl cellulose, ethyl cellulose, etc.

Laminated products may be made by superimposing organic or inorganicfiber sheet materials coated and 0 0 impregnated with the polymericcompositions and thereafter bonding the sheets under heat and pressure.2 Shaped articles formed from such compositions under heat and pressurein accordance with the practices now where Z and R have the meaningsdefined in claim 1. widely used in the plastics art have a number ofwell 4. A compound as in claim 1 having the general forknownapplications such as in the decorative field, mula electrical boardfield, etc.

It will of course be apparent to those skilled in the art. Z Z thatother conditions of reaction in addition to those specifically describedin the foregoing examples may be 0 employed without departing from thescope of the in- Z 0 0 Z vcntion. Thus, it is apparent that many of theconditions outlined previously can be used for making the where Z and Rhave the meanings defined in claim 1.

compositions herein described and claimed. Also, it 5. A compound havingthe formula CN CN will be apparent that the ingredients chosen formaking 6. The compound 4,4-bis(3,4-dicyanophenoxy) bithe desiredreaction products can be varied widely, phenyl. many examples of whichhave been given above. 7. The compound Z-chloro-l,4-bis-(3,4-dicyano-What we claim as new and desire to secure by Letters phenoxy)benzene.Patent of the United States is: 8. The compound4,4'-bis(3,4-dicyanophenoxy) dil. Compounds of the general formulasphenyl sulfone.

1. COMPOUNDS OF THE GENERAL FORMULAS
 2. A compound as in claim 1 whichhas the general formula
 3. A compound as in claim 1 having the generalformula
 4. A compound as in claim 1 having the general formula
 5. Acompound having the formula
 6. The compound4,4''-bis''(3,4-dicyanophenoxy) biphenyl.
 7. The compound2-chloro-1,4-bis-(3,4-dicyanophenoxy)benzene.
 8. The compound4,4''-bis(3,4-dicyanophenoxy) diphenyl sulfone.